Oxidative dehydrogenation in the presence of chlorine



United States Patent 3 308 197 OXIDATIVE DEHSiDRbGENATION IN THE PRESENCE or CHLORINE Laimonis Bajars, Princeton, N.J., assignor to Petro-Tex This application is a continuation-in-part of my copending application Serial Number 249,997 filed January 8, 1963, entitled, Dehydrogenation, now abandoned, which in turn was a continuation-in-part of my now abandoned applications Serial Number 52,776 filed August 30, 1960, entitled, Improved Dehydrogenation Process, Serial Number 145,992 filed October 18, 1961, entitled, Dehydrogenation of Hydrocarbons, Serial Number 145,993 filed October 18, 1961, entitled, Dehydrogenation Process, Serial Number 156,954 filed December 4, 1961, entitled, Process for Dehydrogenation, Serial Number 157,000 filed December 4, 1961, entitled. Method of Dehydrogenation, Serial Number 207,105 filed July 2, 1962, and Serial Number 36,718 filed June 17, 1960, entitled, Dehydrogenation Process.

This invention relates to a process for dehydrogenating organic compounds and relates more particularly to the dehydrogenation of organic compounds in the vapor phase at elevated temperatures in the presence of oxygen, chlorine and an improved inorganic contact mass.

It has been found recently that a great variety of dehydrogenatable organic compounds may be dehydrogenated by reacting a mixture of an organic compound containing at least one pair of adjacent carbon atoms, each of which possess at least one hydrogen atom, chlorine or a chlorine-liberating material, and oxygen under specified conditions at an elevated temperature, and at a reduced partial pressure of the organic compound, in the presence of certain metals or compounds thereof to obtain the corresponding unsaturated organic compound containing at least one or CEC grouping.

I have found, quite unexpectedly, that this process may be improved so that increased selectivities and yields of unsaturated organic compound derivatives containing the c=0 or -CEC-- grouping are obtained more efliciently even with less chlorine and under less stringent process con ditions, when such reaction is conducted in the presence of a contact mass comprising as a first component at least one element of a metal of Groups Ia and IIa (ie the alkali and alkaline earth metals) together with a second component which is a metal or compound thereof of Periodic Table Group IIIb.

The process of this invention can be applied to a great variety of organic compounds to obtain the corresponding unsaturated derivative thereof. Such compounds normally will contain from 2 to 20 carbon atoms, at least one l grouping, that is, adjacent carbon atoms each containing at least one hydrogen atom and having a boiling point below about 350 C. Such compounds may contain in addition to carbon and hydrogen, oxygen, halogens, nitrogen and sulphur. Among the classes of organic com- Periodic Table, e.g., is found in Smiths Introductory gollegfg ghemis'try, 3rd edition (Appleton-Cen-tury=Crofts,

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3,308,197 Patented Mar. 7, 1967 pounds which are dehydrogenated by means of the novel process of this invention are alkanes, alkenes, alkyl halides, ethers, esters, aldehydes, ketones, organic acids, alkyl aromatic compounds, alkyl heterocyclic compounds, cyanoalkanes, cycloalkanes and the like. Illustrative de-' hydrogenation include ethylbenzene to styrene, isopropylbenzene to a-methyl styrene, ethylcyclohexane to styrene, cyclohexane to benzene, ethane to ethylene and acetylene, ethylene to acetylene, propane to propylene, isobutane to isobutylene, n-butane to butene and butadiene-l,3, butene-1 to butadiene-1,3 and vinyl acetylene, cis or trans butene-2 to butadiene-1,3, butane or butene to vinyl acetylene, butadiene-l,3 to vinyl acetylene, methyl butene to isoprene, isobutane to isobutylene, propionaldehyde to acrolein, ethyl chloride to vinyl chloride, propionitrile to acrylonitrile, methyl isobutyrate to methyl methacrylate, and the like. Other representative materials which are readily dehydrogenated in the novel process of this invention include ethyl toluene, the alkyl chlorobenzenes, ethyl naphthalene, isobutyronitrile, propyl chloride, isobutyl chloride, ethyl fluoride, ethyl dichloride, butyl chloride, the chlorofluoroethanes, methylethyl ketone, diethyl ketone, methyl propionate, and the like. This invention is useful in the preparation of vinylidene compounds containing at least one CHFC group, that is, a compound possessing at least one group containing a terminal methylene group attached by a double bond to a carbon atom, and 2 to 12 carbon atoms and is particularly useful in the dehydrogenation of hydrocarbons containing 2 to 5 carbon atoms or aliphatic nitriles of 3 to 4 carbon atoms. Preferred compounds to be dehydrogenated are hydrocarbons of 4 to 8 carbon atoms having at least four contiguous non-quaternary carbon atoms. Aliphatic acyclic hydrocarbons of from 4 to 5 or 6 carbon atoms are preferred. The invention is further particularly adapted to provide butadiene-l,3 from butane and butene and isoprene from isopentane and isopentene in high yields and excellent conversion and selectivity.

As shown by the examples below and the disclosures herein, the novel process of this invention is applicable to a great variety of organic compounds containing 2 to 20 carbon atoms and at least one pair of adjacent carbon atoms bonded together and each carbon atom possessing at least one hydrogen atom including the following: hydrocarbons including both alkanes and alkenes, especially those containing 2 to 6 or 8 carbons; carbocyclic com pounds containing 6 to 12 carbon atoms, including both alicyclic compounds and aromatic compounds of the formula wherein Ar is phenyl or naphthyl, R is hydrogen or methyl and X and Y are hydrogen or alkyl radicals containing 1 to 4 carbon atoms, or halogen; alkyl ketones containing 4 to 6 carbon atoms; aliphatic aldehydes containing 3 to 6 carbon atoms; cyanoalkanes containing 2 to 6 carbon atoms; halo-alkanes and halo-alkenes containing 2 to 6 carbon atoms, particularly chloroand fluoro-alkanes and the like. Vinylidene compounds containing the CH =C group, that is, containing a terminal methylene group attached by a double bond to a carbon atom, are readily obtained from organic compounds containing 2 to 12 carbon atoms and at least one III GH -(l1- group wherein adjacent carbon atoms are singly bonded and possess at least one hydrogen each. For example, vinylidene halides; vinyl esters; acrylic acid and alkyla and halo-acrylic acids and esters; vinyl aromatic compounds; vinyl ketones; vinyl heterocyclic compounds; diolefins containing 4 to 6 carbon atoms, olefins containing 2 to 8 carbon atoms, and the like are obtained as products. The vinylidene compounds normally contain from 2 to 12 carbon atoms and are well known as a commercially useful class of materials for making valuable polymers and copolymers therefrom.

Useful feeds as starting materials may be mixed hydro carbon streams such as refinery streams. For example, the feed material may be the olefin-containing hydrocarbon mixture obtained as the product from the dehydrogenation of hydrocarbons. Another source of feed for the present process is from refinery by-products. Although various mixtures of hydrocarbons are useful, the preferred hydrocarbon feed contains at least 50' weight percent butene-1, butene-2, n-butane and/or butadiene-l, 3 and mixtures thereof, and more preferably contains at least 70 percent n-butane, butene-1, butene-2 and/or butadiene-l, 3 andv mixtures thereof. Any remainder usually will be aliphatic hydrocarbons. The process of this invention is particularly effective in dehydrogenating acyclic aliphatic hydrocarbons to provide a hydrocarbon product wherein the major unsaturated product has the same number of carbon atoms as the feed hydrocarbon.

The chlorine-liberating material may be such as chlorine itself, hydrogen chloride, aliphatic chlorides of 1 to 6 carbon atoms such as methyl chloride or ethylene dichloride, carbon tetrachloride, ammonium chloride and the like. Preferably the chlorine-containing material will either volatilize or decompose at a temperature of no greater than 100 C. to liberate the required amount of chlorine or hydrogen chloride. Usually an amount of at least .005 or 0.01 mol of chlorine per mol of organic compound to be dehydrogenated will be used. It is one of the unexpected advantages of this invention that only very small amounts of chlorine are required. Less than 0.5 mol of chlorine, as 0.2 mol, per mol of organic compound to be dehydrogenated may be employed. Suitable ranges are such as from about .005 or 0.01 to 0.05, 0.1, 0.25 or 0.3 mol of chlorine per mol of the compound to be dehydrogenated. Excellent results are obtained when the chlorine is present in an amount of less than 0.3 mol of chlorine per mol of the compound to be dehydrogenated. It is understood that when a quantity of chlorine is referred to herein, both in the specification and. the claims, that this refers to the calculated quantity of chlorine in all forms present in the vapor space under the conditions of reaction regardless of the initial source or the form in which the chlorine is present. For example, a reference to 0.05 mol of chlorine would refer to the quantity of chlorine present whether the chlorine was fd as 0.05 mol of C1 or 0.10 mol of HCl. Preferably the chlorine will be present in an amount no greater than or mol percent of the total gaseous mixture in the dehydrogenation zone.

The minimum amount of oxygen employed will generally be at least about one-fourth mol of oxygen per mol of organic compound to be dehydrogenated. Large amounts as about 3 mols of oxygen per mol of organic compound may be used. Excellent yields of the desired unsaturated derivatives have been obtained with amounts of oxygen from about 0.4 to about 1.2 or 1.5 mols of oxygen per mol of organic compound and suitably may be within the range of about 0.4 to 2 mols of oxygen per mol of organic compound. Preferably the oxygen will 'be present in an amount of at least 0.4 or 0.6 mol per mol of compound to be dehydrogenated. Oxygen may be supplied to the reaction system as pure oxygen or as oxygen diluted with inert gases such as helium, carbon dioxide, as air and the like. In relation to chlorine, the amount of oxygen employed should be at least 2 mols of oxygen per mol of chlorine and preferably will be at least or greater than 2.50 mols of oxygen per mol of chlorine; A

4 suitable ratio is at least 3.0 mols of oxygen per mol of chlorine.

While the total pressure on systems employing the process of this invention normally will be at or in excess of atmospheric pressure, vacuum may be used. Higher pressures, such as about or 200 p.s.i.g. may be used. The partial pressure of the organic compound under reaction conditions usually will be equivalent to below 10 inches mercury absolute when the total pressure is atmospheric. Better results and higher yields of desired product are normally obtained when the partial pressure of the organic compound is equivalent to less than about one-third or one-fifth of the total pressure. Also because the initial partial pressure of the hydrocarbon to be dehydrogenated is generally equivalent to less than about 10 inches of mercury at a total pressure of one atmosphere, the combined partial pressure of the hydrocarbon to be dehydrogenated plus the dehydrogenated hydrocarbon will also be equivalent to less than about 10 inches of mercury. For example, under these conditions, if butene is being dehydrogenated to butadiene, at no time will the combined partial pressure of the butene and buta-diene be greater than equivalent to about 10 inches of merucry at a total pressure of one atmosphere. Preferably the hydrocarbon to be dehydrogenated should be maintained at a partial pressure equivalent to less than one-third the total pressure, such as no greater than six inches or no greater than four inches of mercury, at a total pressure of one atmosphere. The desired pressure is obtained and maintained by techniques including vacuum operations, or by using helium, organic compounds, nitrogen, steam and the like, or by a combination of these methods. Steam is particularly advantageous and it is surprising that the desired reactions to produce high yields of product are effected in the presence of large amounts of steam. Steam is particularly advantageous to obtain the required low partial pressure of the organic compound in the process. When steam is employed, the ratio of steam to organic compound is normally above about two mols of steam per mol of organic compound such as within the range of about 2 or 5 to 20 or 30 mols, although larger amounts of steam as high as 40 mols have been employed. The degree of dilution of the reactants with steam and the like is related to maintaining the partial pressure of the organic compound in the system at below about one-third atmosphere and preferably below 10 inches mercury absolute when the total pressure on the system is one atmosphere. For example, in a mixture of one mol of butene, three mols of steam and one mol of oxygen under a total pressure of one atmosphere the butene would have an absolute pressure of one-fifth of the total pressure, or roughly six inches of merucry absolute pressure. Equivalent'to this six inches of mercury butene absolute pressure at atmospheric pressure would be butene mixed with oxygen and chlorine under a vacuum such that the partial pressure of the butene is six inches of mercury absolute. A combination of a diluent such as steam together with a vacuum may be utilized to achieve the desired partial pressure of the hydrocarbon. For the purpose of this invention, also equivalent to the six inches of mercury butene absolute pressure at atmospheric pressure would be the same mixture of one mol of butene, three mols of steam and one mol of oxygen under a total pressure greater than atmospheric, for example, a total pressure of 15 or 20 inches mercury above atmospheric. Thus, when the total pressure on the reaction zone is greater than one atmosphere, the absolute values for the pressure of butene will be increased in direct proportion to the increase in total pressure above one atmosphere. Another feature of this invention is that the combined partial pressure of the hydrocarbon to be dehydrogenated plus the chlorine-liberating material will preferably also be equivalent to less than 10 inches of mercury, and preferably less than 6 or 4 inches of mercury, at a total pressure of one atmosphere. The

lower limit of organic compound partial pressure will be dictated by commercial considerations and normally will be greater than about 0.1 inch of mercury absolute.

The temperature of the reaction is from above 400 C. to about 800 C. or 1000 C. Preferably the temperatures will be from at least 450 C. to 900 C., and generally will be at least about 500 C. The optimum temperature may be determined as by thermocouple at the maximum temperature of the reaction. Usually the temperature of reaction will be con-trolled between about 450 C. and about 750 C. or 800 C.

The flow rates of the gaseous reactants may be varied quite widely and good results have been obtained with organic compound gaseous flow rates ranging from about 0.25 to about 3 liquid volumes of organic compound per volume of reactor packing per hour, the residence or contact time of the reactions in the reaction zone under any given set of reaction conditions depending upon the factors involved in the reaction. Generally the flow rates will be within the range of about 0.10 to 25 or higher liquid volumes of the hydrocarbon to be dehydrogenated, calculated at standard conditions of 0 C. and 760 mm. of mercury per volume of reactor space containing catalyst per hour (referred to as either LHSV or liquid v./v./ hr.). Usually the LHSV will be between 0.15 and 15. The volume of reactor containing catalyst is that volume of reactor space including the volume displaced by the catalyst. For example, if a reactor has a particular volume of cubic feet of void space, when that void space is filled with catalyst particles the original void space is the volume of reactor containing catalyst for the purpose of calculating the flow rates. The residence or contact time of the reactants in the reaction zone under any given set of reaction conditions depends upon all the factors involved in the reaction. Contact times ranging from about 0.01 to about two seconds at about 450 C. to 750 C. have been used. A wider range of residence times may be employed, as 0.001 second to about or seconds. Residence time is the calculated dwell time of the reaction mixture in the reaction zone assuming the mols of product mixture are equivalent to the mols of feed mixture.

For conducting the reaction, a variety of reactor types may be employed. Fixed bed reactors may be used and fluid and moving bed systems are advantageously applied to the process of this invention. In any of the reactors suitable means for heat removal may be provided. Tubular reactors of large diameter which are loaded or packed with the solid contact mass are satisfactory.

Good results have been obtained when the exposed surface of the solid con-tact mass is greater than about 25 square feet, preferably greater than about 50 square feet per cubic foot of reactor as 75 or 100 or higher. Of course, the amount of catalyst surface may be much greater when irregular surface catalysts are used. When the catalyst is in the form of particles, either supported or unsupported, the amount of catalyst surface may be expressed in terms of the surface area per unit weight of any particular volume of catalyst particles. The ratio of catalytic surface to weight will be dependent upon various factors including the particle size, particle distribution, apparent bulk density of the carrier, and so forth. Typical values for the surface to weight ratio are such as about /2 to 200 square meters per gram, although higher and lower values may be used.

Excellent results have been obtained by packing the reactor with catalyst particles as the method of introducing the catalytic surface. The size of the catalyst particles may vary widely but generally the maximum particles size will at least pass through at Tyler Standard Screen which has an opening of 2 inches, and generally the largest particles of catalyst will pass through a Tyler Screen with one inch openings. Thus, the particle size when particles are used preferably will be from about 10 microns to a particle size which will pass through a Tyler Screen with openings of 2 inches. If a carrier is used the catalyst may be deposited on the carrier by methods known in the art such as by preparing an aqueous solution or dispersion of the catalyst, mixing the carrier with the solution or dispersion until the active ingredients are coated on the carrier. The coated particles may then be dried, for example, in an oven at about 110 C. Various other methods of catalyst preparation known to those skilled in the art may be used. Very useful carriers are the Alundums, silicon carbide, the Carborundums, pumice, kieselguhr, asbestos, and the like. When carriers are used, the amount of catalyst composition on the carrier will generally be in the range of about 2 to weight percent of the total weight of the active catalytic material plus carrier. Another method for introducing the required surface is to utilize as a reactor a small diameter tube wherein the tube wall is catalytic or is coated with catalytic material. If the tube wall is the only source of catalyst generally the tube will be of an internal diameter of no greater than one inch such as less than inch in diameter or preferably will be no greater than about /2 inch in diameter. The technique of utilizing fluid beds lends itself Well to the process of this invention.

In the above descriptions of catalyst compositions, the composition described is that of the surface which is exposed in the dehydrogenation zone to the reactants. That is, if a catalyst carrier is used, the composition described as the catalyst refers to the composition of the surface and not to the total composition of the surface coating plus carrier. The catalystic compositions are intimate combinations or mixtures of the ingredients. These ingredients may or may not be present as alloys. Catalyst binding agents or fillers may be used, but these will not ordinarily exceed about 50 percent or 65 per- .cent by weight of the catalytic surface. The defined catalytic components will be the main active constituents in the catalyst and the catalyst may consist essentially of the defined catalytic components. The weight percent of the defined catalytic atoms will generally be at least 20 percent, and are preferably at least 35 percent of the composition of the catalyst surface exposed to the reaction gases and will generally be at least 51 or about 80 atomic weight percent of any cations in the surface, such as at least 80 atomic percent of any metal cations in the surface.

The defined catalyst combinations may be employed in any form, e.g., as pellets, tablets, as coatings on carriers or supports, and the like, in both fixed and fluidized beds. Other methods of catalyst preparation known to those skilled in the art may also be used.

According to this invention, the catalyst is autoregenerative and thus the process is continuous. Little or no energy input is required for the process and it may be operated essentially adiabatically. Moreover, small amounts of tars and polymers are formed as compared to prior art processes. It is also an advantage of this invention that triple bond containing compounds are more easily obtained than with catalysts containing only one of the defined components.

In the examples given below the conversions, selectivities and yields are expressed as mol percent based on the mols of the compound to be dehydrogenated fed to the reactor. The temperature of reaction listed is approximately the maximum temperature in the reactor. The catalysts are present as fixed beds.

The Group Ia and 11a compounds used include, for example, oxides, hydroxides and salts such as the phosphates, sulfates, halides and the like. Useful compounds include, for example, lithium chloride, lithium oxide, lithium bromide, lithium fluoride, lithium phosphate, sodium hydroxide, sodium oxide, sodium chloride, sodium sulfate, beryllium oxide, sodium bromide, sodium iodide,

sodium phosphate, sodium fluoride, potassium chloride, potassium bromide, potassium sulfate, potassium iodide, potassium nitrate, potassium citrate, potassium hydroxide, potassium oxide, potassium phosphate, rubidium chloride, rubidium bromide, rubidium iodide, rubidium oxide, magnesium acetate, magnesium bromide, magnesium oxide, magnesium iodide, calcium oxide, calcium acetate, calcium oxalate, calcium chloride, calcium bromide, calcium iodide, calcium phosphate, calcium fluoride, strontium hydroxide, strontium chloride, strontium bromide, barium oxide, barium chloride, barium hydroxide, barium sulfate, barium bromide, barium iodide, beryllium chloride, and the like, and mixtures thereof. Preferred Group Ia and H11 metal elements are lithium, sodium, magnesium, potassium, calcium strontium and barium, such as the oxides, phosphates, iodides, bromides, chlorides or fluorides of these metals. The oxides and halides and mixtures thereof are particularly preferred. Many of the Group Ia and 11a compounds may change during the preparation of the catalyst, during heating in a reactor prior to use in the process of this invention, or are converted to another form under the described reaction conditions, but such materials still function as an effective compound in the defined process. For example, the halides may be converted to the oxides or vice versa under the conditions of reaction. The amount of Group Ia metal compound or Group IIa metal compound with the additional metal or inorganic compound thereof may be varied quite Widely and while small amounts, as low as one-tenth percent based on the total catalyst, have been used, much larger amounts may be employed in concentrations up to where the Group Ia or IIa metal compound is the larger constituent in the composition, such as up to 50 weight percent or more, as 95 percent. Normally up to 50 percent, and more usually about one to about twenty-five percent of the Group Ia or Group lIa compound, such as about one to ten percent, with the remainder being the defined second inorganic metal compound, is satisfactory. On an atomic basis, the combined amount of the metal atoms of Group In and/r IIa will be from at least about 0.001 atom per atom of the defined second catalyst component and mixtures thereof. Excellent results are obtained at ratios of about 0.01 to 1.0 or 1.5 atoms of Group Ia. and 11a per atom of the elements from the second specified group, such as from or about 0.01 or 0.02 to 0.5 atom of Group In and Hit per atom of the elements from the second specified group.

A great variety of metals or metal compounds of H111, may be used as the second component in conjunction with the Group Ia and IIa metal compounds. Metals of the described second component group in elemental forms may be employed and are included within the scope of this invention. The metals generally are changed to inorganic compounds thereof, at least on the surface, under the reaction conditions set forth herein. Particularly effective are inorganic compounds such as the oxides and salts including the phosphates and the halides, such as the iodides, bromides, chlorides and fluorides. Inorganic compounds which are useful as the second component in the compounded contact mass for the process of this invention include scandium bromide, lanthanum oxide, yttrium oxide, cerium bromide, ceric oxide, ceric chloride, cerium phosphate, thorium dioxide, or uranium dioxide, and mixtures thereof. Particularly useful are mixed or pure rare earth chlorides, oxides and hydrates such as Lindsay ceric oxides Code 210B (e.g., 90% CeO 4% other rare earths, 1% P 0 1.0% SiO and other minor ingredients); Lindsay ceric oxide Code 217 (e.g., 99.9% cerium oxide); didymium chlorides, hydrates, nitrates or oxides (e.g., 4556% La O 1-2% CeO Pr O Nd O Sm O Gd O 0.4% Y O and 12% other rare earth oxides). Preferably the catalyst will be solid under the conditions of reaction. Excellent catalysts are those comprising atoms of cerium, thorium and uranium, such as the oxides, phosphates, iodides, bromides, chlorides or fluorides of these elements. As the second component the rare earth compounds, such as the oxides or halides, are preferred. Many of the salts, oxides and hydroxides of the metals may change during the preparation of the catalyst, during heating in a reactor prior to use in the process of this invention, or are converted to another form under the described reaction conditions, but such materials still function as an eflective compound in the defined process. For example, many of the metal nitrates, nitrites, carbonates, hydroxides, acetates, and the like, may be converted to the corresponding oxide or chloride under the reaction conditions defined herein. Salts which are stableor partially stable at the defined reaction temperatures are likewise effective under the conditions of the described reaction, as well as such compounds which are converted to another form in the reactor. At any rate, the catalysts are effective if the defined catalysts are present in a catalytic amount in contact with the reaction gases. Useful catalyst combinations include cerium oxide and calcium chloride, cerium oxide and calcium oxide, cerium oxide and magnesium oxide, calcium chloride with magnesium oxide and cerium oxide, cerium oxide and potassium chloride, cerium oxide and strontium hydroxide, cerium oxide and sodium chloride, cerium oxide with magnesium oxide and calcium oxide, cerium oxide and barium hydroxide, ceric oxide and sodium hydroxide, cerium oxide and barium oxide, cerium oxide and lithium chloride, and potassium bromide combined with didymium oxide or rare earth oxides.

In Examples 1 to 17 a tubular Vycor 3 reactor, filled with the described solid contact masses, equipped with an external electric furnace is used. The reaction conditions and the active materials used are set forth in the specified Examples. The organic compound and oxygen are added at the top of the reactor, the chlorine is added to this stream as it enters the reactor and the steam is added separately opposite this stream. The results are reported as mol percent conversion, selectivity and yield of desired unsaturated product per pass. All other percentages are by weight percent, unless expressed otherwise.

Example I A contact mass containing 97.5 percent ceric oxide and 2.5 percent lithium chloride is prepared by stirring ceric oxide into water which contains 2.5 percent lithium chloride based on the eerie oxide, adding 4 to 8 mesh AMC 4 pellets to the slurry and depositing the ceric oxide and lithium chloride onto the pellets by heating and stirring the mixture. The coated pellets are dried and placed in the Vycor reactor to a bed depth of eight inches. The reactants in a molar ratio of one mol of butene, 15 mols of steam, 0.85 mol of oxygen, and 0.115 mol of chlorine (added as 37 percent hydrochloric acid) are fed to the reactor at a flow rate of butene of one-sixth liquid v./v./hr. and the reactor is maintained at a temperature of about 650 C. The butene is converted to butadiene- 1,3 at a conversion of 78 percent and selectivity of 76 percent for a yield per pass of 59 percent.

Example 2 When butene is dehydrogenated under the same conditions of Example 1 with a solid contact mass consisting of ceric oxide only deposited on the AMC pellets, the yield of butadiene-1,3 per pass is about 43 percent, thus, demonstrating the unexpectedly large increase in yield of butadiene-l,3 obtained with the combined catalyst even though the catalyst contains only 2.5 percent lithium a Vycor is the trade name of Corning Glass Works, Corning, N.Y., and is composed of approximately 96 percent silica with the remainder being essentially B203.

4 Supplied by the Carborundum Company, type AMC pellets are poly-surface pellets of fused aluminum oxide characterized as having medium porosity (40-50 percent), coarse grain and 300-350 micron pore size.

chloride. When this example is repeated and the flow rate of butene is one-half liquid v./v./hr. equivalent results are obtained. When Example 1 is repeated at 650 C. with a 95 percent ceric oxidepercent lithium chloride contact mass and the same reaction conditions set forth above, isobutylene is obtained from isobutane, acrylonitrile from propionitrile, acrolein from propionaldehyde, isoprene from Z-methyl butene-2, styrene from ethylbenzene, vinyl chloride from ethyl chloride, ethylene from ethane, styrene from ethylcyclohexane and methyl isopropenyl ketone from methyl isopropyl ketone in good yields.

Example 3 Butene is dehydrogenated over a contact mass containing 97.5 percent ceric oxide and 2.5 percent calcium chloride prepared by evaporating a slurry of ceric oxide and calcium chloride onto 4 to 8 mesh AMC pellets as described above. dried contact mass in the Vycor reactor in a molar ratio of one mol of butene, 15 mols of steam 0.85 mol of oxygen and 0.115 mol of chlorine (provided in the form of 37 percent hydrochloric acid) at a flow rate of butene of one-sixth liquid v./v./hr. and the reactor is maintained at a temperature of 650 C. Butadiene-l,3 is obtained in a yield of 55 percent per pass at a conversion of 65 percent and selectivity of 85 percent. Another run made with a similar contact mass containing 90 percent ceric oxide and 10 percent calcium chloride also results in good yields of butadiene-1,3.

Example 4 For dehydrogenating butene, 6 mm. Vycor Raschig rings are coated with ceric oxide containing 3 percent calcium oxide and one percent magnesium oxide from a water slurry thereof, dried and placed in a tubular Vycor reactor to a depth of 8 inches. The reactants in amolar ratio of mols of steam, 0.85 mol of oxygen and 0.115 mol of chlorine (fed as a 37 percent HCl water solution) per mol of butene-2 are fed to the reactor at a flow rate of butene-2 of one-half liquid v./v./hr. and the reactor is maintained at a temperature of 600 C. A yield per pass of 67 percent butadiene-1,3 at a conversion of 77 percent and selectivity of 87 percent is obtained.

Example 5 When Example 4 is repeated with the Vycor Raschig rings having coated thereon 99.9 percent purity ceric oxide under the same reaction conditions, the yield of butadiene-l,3 is less than that obtained when the catalyst contained calcium oxide and magnesium oxide.

When Example 1 above is repeated at 650 C. using the same reactor set-up and ceric oxide containing one percent magnesium oxide and three percent calcium oxide on Vycor rings as the reactor packing, acrylonitrile is obtained from propionitrile, styrene from ethylbenzene, isobutylene from isobutane, isoprene from 2-methyl butene-2, vinyl chloride from ethyl chloride, ethylene from ethane, methyl isopropenyl ketone from methyl isopropyl ketone, a-methyl styrene from isopropyl benzene, and acrolein from propionaldehyde in good yields.

Examples 6 through 13 The 99.9 percent purity ceric oxide of Example 5 is mixed with varying amounts of the following alkali and alkaline earth compounds in water slurries, deposited on Vycor Raschig rings in the reactor described in Example 4 and air dried. Calcium and strontium are added as the nitrates and converted to the oxides by heating with air. Potassium, sodium and lithium are added as the hydroxides. The molar -ratio of reactants used is 15 mols of steam, 0.85 mol of oxygen and 0.17 mol of chlorine (fed :as aqueous hydrogen chloride) per mol of butene-2, which The reactants are passed over the Ex- Temp., Conver- Seleetiv- Yield, ample Coating C. sion, ity, Percent Percent Percent COz+3% KOH... 650 63 63 40 (ROM-3% NaOH 650 70 73 51 CeO2+2.5% LiOH 550 50 90 45 CeOz+2.5% Li0H., 600 64 85 55 CeOz+2.5% LiOH. 625 G8 Geog-{4% CaO. 650 60 83 49 oeo2+4% Oa0 675 72 73 53 oeo2+4% $10"... 625 56 71 40 Examples 14 through 17 Samples of South African monazite ore which contain 48 percent cerium oxide, and South Carolina monazite ore which contains 44 percent cerium oxide are used as described below after being compounded with sodium hydroxide and lithium hydroxide in the amounts set forth in the table below. The ores are suspended in water and sodium hydroxide and lithium hydroxide added thereto after which the dispersions are coated on 6 mm. Vycor Raschig rings which are dried in a stream of air in a Vycor reactor. The ratio of reactants used is 15 mols of steam, 0.85 mol of oxygen and 0.115 mol of chlorine (fed as hydrogen chloride) per mol of butene-2. The butene-2 flow rate is one-half liquid v./v./hr. and the reactor is maintained at a temperature of 600 C. with the exception of Run 17 which is at 650 C.

In each case an increase in yield of butadiene-1,3 is obtained as compared to the uncompounded ores.

Examples 18 and 19 T 0 further show the elfect of the combination catalyst containing a metal element from Group Ia and IIa together with an element of the defined second component comparative examples are made.

The runs are made in a Vycor reactor which is one inch internal diameter; the overall length of the reactor is about 36 inches with the middle 24 inches of the reactor being encompassed by a heating furnace; the bottom 6 inches of the reactor is empty; at the top of this 6 inches in a retaining plate, and on top of this plate are placed 16 inches of the catalyst particles. The catalyst particles are prepared by coating the designated catalytic compounds on A x 4 inch Vycor Raschig rings by pouring a thin aqueous slurry of the catalytic compound through the 16 inches of rings contained in the reactor. This procedure is repeated several times until the rings are thoroughly coated with the catalyst. The coated rings are then dried in the reactor under a stream of nitrogen at a reactor temperature of approximately 500 C. On top of the dried catalyst particles are placed 6 inches of uncoated 1 x 4 inch Vycor Raschig rings to form a preheat zone. The

flow rates are calculated on the volume of the 16 inch long by one inch diameter portion of the reactor which was at or near the reaction temperature and is filled with catalyst particles. At a 700 C. maximum bed temperature, butene-Z of a purity of at least 99 mol percent is dehydrogenated to butadiene-1,3. The flow rate of butene-2 is maintained at one liquid volume of butene-2 (calculated at C. and 760 mm. mercury) per volume of the 16 inch section of the reactor packed with catalyst which was at or near the reaction temperature per hour (liquid v./v./hr.). The flow rate of butene-2 is 0.22 liter per minute (calculated at 0 C. and 760 mm. mercury). Oxygen and steam are also fed to the reactor at a mol ratio of oxygen of butene-2 of 0.85, and a mol ratio of steam of butene-Z of 16. Hydrogen chloride is added as a 13 weight percent aqueous solution at a rate which is equivalent to 0.3 8 mol of chlorine (calculated as C1 per mol of butene-2. The steam, butene-2, oxygen and aqueous solution of hydrogen chloride .are added at the top of the reactor. ported as mol percent, the percent selectivity to butadiene- 1,3 and the resulting yields of butadiene-1,3 are reported as mol percent of butadiene-1,3 based on the amount or" butene-2 fed to the reactor.

Example 18 The catalyst is La O The conversion is 64 percent, the selectivity is 34 percent and the yield is 22 percent.

Example 19 Example 18 is repeated with the exception that the catalytic coating on the Vycor rings consists of by weight 95 percent La O and percent CaO. The conversion is 56 percent, the selectivity is 55 percent and the yield is 31 percent.

Example 20 Butene-2 is dehydrogenated at 625 C. using 7.5 mols of steam, 1.25 mol of oxygen and 0.09 mol of chlorine (fed as HCl) respectively per mole of butene. The flow rate is 1.0 liquid hourly space velocity. The catalyst is a cerium hydrate (Lindsay 201) containing by weight (calculated as the oxides) approximately 76% cerium oxide, 4% other rare earth oxides, .25 thorium oxide, minor amounts of other elements, and 2% by weight calcium oxide. The conversion is 67 mol percent, the selectivity is 79 percent and the yield per pass is 53 percent butadiene.

Example 21 Isobutane is dehydrogenated to isobutylene employing mols steam, 1.0 mol oxygen and 0.11 mol chlorine per mol of isobutane. The catalyst is of the same composition as used in Example 20. Isobutylene is obtained at a selectivity of 60 mol percent at a temperature of 550 C.

Example 22 Example 21 is repeated at 600 C. substituting propane for the isobutane. Propylene is obtained at a selectivity of 68 percent per pass.

The process of this invention is particularly applicable to the dehydrogenation of hydrocarbons, including dehydroisomerization and dehydrocyclization, to form a variety of acyclic compounds, cyclo aliphatic compounds, aromatic compounds and mixtures thereof. For example, 2-ethylhexene-1 may be converted to a mixture of aromatic compounds such as toluene, ethyl benzene, p-xylene, o-xylene and styrene.

I claim:

1. The method for dehydrogenating hydrocarbon compounds having 2 to carbon atoms to produce a dehydrogenated product having the same number of carbon atoms and the same structure with the exception of the removed hydrogen atoms which comprises heating in the The conversion of butene-2 is revapor phase at a temperature of above 400 C. the said hydrocarbon compound having a group with oxygen in a molar ratio of greater than onefourth mol of oxygen per mol of said hydrocarbon compound, chlorine in an amount of less than 0.3 mol of chlorine per mol of said hydrocarbon compound and in an amount of no greater than 10 mol percent of the total gaseous mixture in the dehydrogenation zone, the ratio of the mols of said oxygen to the mols of said chlorine being at least 2.0, the partial pressure of said hydrocarbon compound being equivalent to less than one-half the total pressure in the presence of a catalyst comprising as its main active constituent (1) a compound selected from the group consisting of oxides, salts and hydroxides of alkali and alkaline earth metals and mixtures thereof, and (2) an inorganic compound of a metal selected from the Periodic Table Group Illb the atoms of the said alkali and alkaline earth metals of (1) being at least about 0.001 atom per atom of the said metals of Group 111]) and further the said 1) being present in an amount of up to 50 weight percent of the total weight of the said (1) and (2) with the weight percent of the cations of the defined (1) and (2) being at least 51 percent of any cations in the catalyst surface exposed to the reaction gases.

2. The method of claim 1 wherein the said hydrocarbon compound is a hydrocarbon having from 2 to 12 carbon atoms.

3. The method of claim 1 wherein the said hydrocarbon compound is an acyclic aliphatic hydrocarbon of 4 to 6 carbon atoms.

4. The method of claim 1 wherein the said hydrocarbon compound is a hydrocarbon selected from the group consisting of n-butene, n-butane, isopentene, isopentane and mixtures thereof.

5. The method of claim 4 wherein the said temperature is at least 450 C.

6. The method of claim 4 wherein steam is employed in the said vapor phase in an amount of from 2 to 30 mols of steam per mol of said hydrocarbon.

7. The method of claim 4 wherein the oxygen is present in an amount of greater than 3.0 mols of oxygen per mol of said chlorine and the said chlorine is present in an amount of from .005 to 0.25 mol of chlorine per mol of said hydrocarbon.

8. The method of claim 1 wherein the alkali and alkaline earth metal compounds are present in an amount of from about .01 to 0.5 atom of the alkali or alkaline earth metal elements per atom of the metal elements of the said 2).

9. A method for dehydrogenating hydrocarbons containing 4 to 5 carbon atoms which comprises reacting in the vapor phase at a temperature between 400 C. and about 750 C. an aliphatic hydrocarbon containing 4 to 5 carbon atoms with oxygen in a molar ratio of about 0.4 mol to about 2 mols of oxygen per mol of hydrocarbon, and above 0.001 mol to less than 0.2 mol per mol of aliphatic hydrocarbon of chlorine, at a partial pressure of said hydrocarbon of less than about one-third the total pressure in the presence of a mixture of (1) a compound selected from the group consisting of alkali metal oxides, alkaline metal hydroxides, alkaline earth metal oxides and alkaline earth metal hydroxides, and (2) an inorganic compound selected from the group consisting of metals of Periodic Table Group III!) and mixtures thereof the said 1) being present in an amount of from about one to twenty-five weight percent of the total weight of the (1) and (2) with the total weight percent of the cations of the said (1) and (2) being at least 51 percent of any cations in the catalyst surface.

10. The method of claim 1 wherein the said (1) is selected from the group consisting of lithium, sodium, magnesium, potassium, calcium, strontium, barium and mix- 13 14 tures thereof and the said (2) is selected from the group OTHER REFERENCES conslstmg of e earth ccfmpounds- Ladoo et al.: Nonmetallic Minerals, published by 11. The method of clalrn 10 wherem the send (1) and M G J-Iiu k C0,, New York 9 P (2) are present as oxides or halides. relied on.

5 Refeences by Examme' DELBERT E. GANTZ, Primary Examiner.

UNITED STATES PATENTS G. E. S CHMITKONS, Assistant Examiner. 3,108,144 10/1963 Tallman 260666 

1. THE METHOD FOR DEHYDROGENATING HYDROCARBON COMPOUNDS HAVING 2 TO 20 CARBON ATOMS TO PRODUCE A DEHYDROGENATED PRODUCT HAVING THE SAME NUMBER OF CARBON ATOMS AND THE SAME STRUCTURE WITH THE EXCEPTION OF THE REMOVED HYDROGEN ATOMS WHICH COMPRISES HEATING IN THE VAPOR PHASE AT A TEMPERATURE OF ABOVE 400*C. THE SAID HYDROCARBON COMPOUND HAVING A >CH-CH< GROUP WITH OXYGEN IN A MOLAR RATIO OF GREATER THAN ONEFOURTH MOL OF OXYGEN PER MOL OF SAID HYDROCARBON COMPOUND, CHLORINE IN AN AMOUNT OF LESS THAN 0.3 MOL OF CHLORINE PER MOL OF SAID HYDROCARBON COMPOUND AND IN AN AMOUNT OF NO GREATER THAN 10 MOL PERCENT OF THE TOTAL GASEOUS MIXTURE IN THE DEHYDROGENATION ZONE, THE RATIO OF THE MOLS OF SAID OXYGEN TO THE MOLS OF SAID CHLORINE BEING AT LEAST 2.0, THE PARTIAL PRESSURE OF SAID HYDROCARBON COMPOUND BEING EQUIVALENT TO LESS THAN ONE-HALF THE TOTAL PRESSURE IN THE PRESENCE OF A CATALYST COMPRISING AS ITS MAIN ACTIVE CONSTITUENT (1) A COMPOUND SELECTED FROM THE GROUP CONSISTING OF OXIDES, SALTS AND HYDROXIDES OF ALKALI AND ALKALINE EARTH METALS AND MIXTURES THEREOF, AND (2) AN INORGANIC COMPOUND OF A METAL SELECTED FROM THE PERIODIC TABLE GROUP IIIB THE ATOMS OF THE SAID ALKALI AND ALKALINE EARTH METALS OF (1) BEING AT LEAST ABOUT 0.001 ATOM PER ATOM OF THE SAID METALS OF GROUP IIIB AND FURTHER THE SAID (1) BEING PRESENT IN AN AMOUNT OF UP TO 50 WEIGHT PERCENT OF THE TOTAL WEIGHT OF THE SAID (1) AND (2) WIHT THE WEIGHT PERCENT OF THE CATIONS OF THE DEFINED (1) AND (2) BEING AT LEAST 51 PERCENT OF ANY CATIONS IN THE CATALYST SURFACE EXPOSED TO THE REACTION GASES. 